JPH04218542A - Flame-retardant polymer composition - Google Patents

Abstract

PURPOSE: To obtain flame resistant polymer compositions, especially olefinic polymers and/or copolymers, containing 8-45 wt.% of a flame retardant system.

CONSTITUTION: A flame retardant system comprises at least one kind of phosphorus component and at least one kind of monomeric triazinylpiperazine; the phosphorus component is free-flowing, powdery, and poorly water-soluble ammonium polyphosphate, while powdery bis-triazinylpiperazone is used as the triazinylpiperazine.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to flame-retardant polymer compositions, preferably olefin polymer and/or copolymer compositions.

0002

[Prior Art] From U.S. Pat. No. 3,810,862,
It is known to use ammonium polyphosphates, mixtures of melamine and dipentaerythritol or mixtures of melamine pyrophosphate and dipentaerythritol to impart flame retardancy to polyolefins.

According to US Pat. No. 4,312,805, a self-extinguishing composition based on polypropylene contains ammonium polyphosphate, melamine and polyamide 6.

Self-extinguishing polyolefins according to US Pat. No. 4,198,493 contain ammonium polyphosphate, cyanuric acid and tris(2-hydroxyethyl)isocyanurate as flame retardants.

Finally, European Patent No. 115,871
Self-extinguishing olefin polymers and copolymers containing ammonium phosphate or amine phosphate and a nitrogen-containing water-insoluble compound, which may consist of poly(triazinyl-piperazine), are known from No. There is.

[0006]

Owing to the relatively low molecular weight of the monomeric triazinylpiperazine, a gradual migration from the polymer matrix and thus an increasing deterioration of its flame retardancy was expected. However, it is surprising that the mixture of ammonium polyphosphate and the triazinylpiperazine monomer already exhibits a remarkable flame retardant effect, especially in olefinic polymers and/or copolymers, which also shows long-term stability. It was found that the

[0007]

More specifically, the present invention provides a flame retardant system (Flammschutzs) consisting of at least a phosphorus component and the monomeric triazinyl-piperazine.
system) 8 to 45% by weight, the phosphorus component being free-flowing, sparingly water-soluble ammonium polyphosphate in powder form, and the phosphorus component being powdered bis-
The present invention relates to a flame-retardant polymer composition characterized in that it uses triazinylpiperazine.

Furthermore, the flame-retardant polymer composition according to the invention may furthermore optionally include the following embodiments: a)
The flame retardant system of the invention may additionally contain tris(2-hydroxyethyl)isocyanurate, pentaerythritol, dipentaerythritol, melamine cyanurate, melamine,
containing a powdered co-synergist selected from the group consisting of melamine pentate, piperazine pyrophosphate, dicyandiamide and cellulose; b) up to 7% by weight of co-synergist with respect to the flame retardant polymer composition; c) the flame retardant system is additionally 3
up to % by weight of a material selected from the group consisting of polyester, polyamide, polyacrylonitrile, polybenzimidazole, polyphenylene sulfide and polytetrafluoroethylene in the form of a fine powder with a particle size of 10 μm or less d) the flame retardant system is additionally 3 related to the flame retardant polymer composition;
up to % by weight of at least one oxide, hydroxide or carbonate of a metal or metalloid in powder form; e) a powdered oxide, hydroxide or carbonate of a metal or metalloid; the salt has a particle size of 0.01 to 10 μm; f) the flame retardant system additionally contains 2 with respect to the flame retardant polymer composition;
% by weight of at least one stabilizer selected from the group consisting of polynuclear phenols, dialkyl sulfides and aromatic phosphites; g) the flame retardant system additionally comprises a flame retardant polymer composition; containing up to 1% by weight of calcium stearate; h) formula (NH
Ammonium polyphosphate represented by 4PO3)n has a chain length n of 200 to 1000, preferably 700,
Phosphorus content of 31.5 ± 0.5% by weight, 14.5 ± 0.5
% nitrogen content by weight and a water-soluble fraction of not more than 10%--measured in a 10% aqueous suspension at 25°C.
(R) Exolit 422]; i) Ammonium polyphosphate of the formula (NH4PO3) n having a chain length n of 200 to 1000, preferably 700 is microencapsulated with melamine/pormamide resin. , and a phosphorus content of 29.0±1%, a nitrogen content of 16.5±1% and ─25℃
As measured in a 10% aqueous suspension of
t) 462]; j) the flame retardant system contains from 5 to 30% by weight of ammonium polyphosphate with respect to the flame retardant polymer composition; k) the general formula

[0009]

[C4]

(wherein, represents a phenyl or naphthyl group or a C7-C18-aralkyl group substituted with an inert group; R2 and R3 are independently C1-C3-
Alkyl group, C5-C18-cycloalkyl group,
represents a phenyl or naphthyl group, optionally substituted with an inert group, or represents a C7-C18-aralkyl group, or NR2 R3 has the formula

[0011]

[C5]

Piperidinyl represented by or formula

001
3]

[C6]

using bis-triazinylpiperazine (representing morpholinyl);
l) N,N'-bis(2,4-dimethoxy-1,
using 3,5-triazin-6-yl)piperazine; m) using N,N'-bis(2,4-diethoxy-1,3,5-triazin-6-yl)piperazine; n )N,N'- bis(2,4-
Dimorpholinyl-1,3,5-triazine-6
o) using 3 to 15% by weight of bis-triazinyl-piperazine with respect to the flame-retardant polymer composition.

Bis-triazinylpiperazine having a particle size of less than 80 μm is preferably used.

The polymers provided with the flame retardant system according to the invention may be: polyethylene, polypropylene, polybutene-1, polymethylpentene-1, ethylene-propylene-copolymers, ethylene and propylene with dienes. Terpolymers with; polystyrene, polymethylstyrene; polypropylene and polyethylene;
A mixture of polypropylene and polybutene-1, butadiene-acrylonitrile copolymer and styrene-butadiene copolymer; polyvinyl chloride,
Polyacrylate, polymethacrylate, polyethyl acrylate and their mutual copolymers and other vinyl compounds (acrylonitrile-butadiene-
Copolymers with styrene, acrylonitrile, styrene and acrylonitrile-styrene-acrylic ester copolymers; cellulose acetate, cellulose nitrate; phenol, urea or melamine
formaldehyde resin, polyamide, polyester,
Polyformaldehyde, polycarbonate.

When producing flame-retardant polymer compositions, it is an object of the invention to distribute the flame retardant system in the polymer as homogeneously as possible. In the case of thermoplastic resins, each component is vigorously mixed in a finely dispersed form for this purpose.
The mixture is then extruded and granulated.

[0018]

EXAMPLES In Examples A, B and C the preparation of bis-triazinylpiperazines which can be used according to the invention is described, while Examples 1 to 2 listed in Tables 1 to 5
No. 7 encompasses flame retardant polymer compositions according to the present invention. Example A N,N'-bis(2,4-dimethoxy-1,3,
Production of 5-triazin-6-yl)piperazine 550 ml of methanol, 55 ml of water, tetra-hydrogen sulfate
n-butylammonium 0.25g and NaHCO
3 1 mol and while maintaining a maximum reaction temperature of 30°C, add 0.5 mol of cyanuric chloride in small quantities;
At this time, the pH was adjusted to 5 to 8. 40 at room temperature
After stirring for a minute, it was heated to reflux. An aqueous solution of piperazine (13% by weight; 0.275 mol) and soda (20% by weight; 0.275 mol) was then added dropwise thereon. The reaction mixture was stirred at room temperature for 1 hour and heated under reflux for 2 hours. After cooling, it was neutralized using dilute sulfuric acid. After filtration, the residue was washed with water. After drying, a finely crystalline white powder was obtained. Yield: 87.2% of theory Melting point: 229-232°C (under decomposition) Elemental analysis: (C
14H20N8 O4) Actual value: C45.78
%; H5.70%; N31.18% Calculated value: C46.15%; H5.53%; N30.75
% Example B N,N'-bis(2,4-diethoxy-1,3,
Preparation of 5-triazin-6-yl)piperazine In a mixture of 400 ml of ethanol and 40 ml of water, Na
1 mol of HCO3 and 0.5 g of tetra-n-butylammonium hydrogen sulfate are suspended and 0.5 mol of cyanuric chloride is added such that the reaction temperature does not exceed 30°C and the pH value is in the range 5 to 8. was gradually added in small amounts. After stirring for 60 minutes at room temperature, the
Heated for 0 minutes. Next, 0.275 mol each of piperazine and soda were simultaneously dissolved in water at room temperature (
12 or 20% by weight). The reaction mixture was stirred at room temperature for 1 hour and then heated under reflux for 3 hours. After cooling, it was filtered and the residue was washed with water and dried to constant weight. As a result, a fine crystalline white powder was obtained. Yield: 81% of theory Melting point: 189-193°C (under decomposition) Elemental analysis: (C
18H28N8 O4) Actual value: C50.98
%; H6.30%; N27.12% Calculated value: C51.42%; H6.71%; N26.65
% Example C N,N'-bis(2,4-dimorpholinyl-1,
Preparation of 3,5-triazin-6-yl)-piperazine The following preparation was carried out under nitrogen. 0.5 mol of cyanuric chloride is suspended in a mixture consisting of 2 l of water and 1 kg of ice, and at the same time 1 mol of morpholine and N
0.5 mol of aOH (as an aqueous solution containing 10% by weight) was added dropwise. The addition was done gradually so that the pH value was maintained between 5 and 10. After stirring for 30 minutes at 25° C., a further 0.5 mol of NaOH (as an aqueous solution containing 10% by weight) was added dropwise. The reaction mixture was heated to 80°C for 90 minutes. After cooling to room temperature, 0.28 mol of piperazine and 0.56 mol of NaOH (
(as an aqueous solution containing 10% by weight) was added dropwise. Finally it was heated under reflux for 12 hours. After cooling, it was filtered and the residue was washed with water and dried. A finely crystalline white powder was obtained. Yield: 98.4% of theory Melting point: 317-321°C (under decomposition) Elemental analysis: (C
26H40N12O4) Actual value: C52.94
%; H7.23%; N28.93% Calculated value: C53.41%; H6.89%; N28.75
% flame-retardant polymer composition is prepared by mixing the components in a SPANGENBERG high-intensity mixer and extruding the mixture in a WEBER compact extruder (screw diameter 20 mm) from 180 to 200 %.
Extrusion at 00°C and DREHER
) - Granulated using a laboratory granulator. Then,
500 g of the granules produced in this way were heated with water vapor in a BECK
ER-VAN-HUELLEN) - using a press 19
1.6 mm thickness at 5°C and 300 bar pressure
It was molded into a test plate.

[0019] Length 127 mm from the above test plate
A specimen with a width of 12.7 mm was cut out. The combustion characteristics of this test specimen were evaluated by Underwriters Laboratories (U
NDERWRITERS LABORATORIES)
Regulations: “Flammability test of plastic materials (Test
for Flammability of Plas
tic Material) - UL94" (May 2, 1975 edition), while their oxygen index (
Sauerstoffindex) ASTM-2
863.

The results of the combustion tests are listed in the last two lines of Tables 1 to 4. The indices in Tables 1 to 4 have the following meanings: 1) HOECHST AG, Frank
furt) polypropylene powder 55g/10mi
Melt index of n (MFI230/5) 3) Hostanox ((R) Hostanox)
0.3 (stabilizer based on polynuclear phenols; manufactured by Hoechst) 0.16% Hostanox ((R) Host
anox) E10 (stabilizer based on dialkyl sulfide; manufactured by Hoechst) 0.16% Hostanox ((R) Hostanox) PA
Mixture consisting of 0.16% R24 (stabilizer based on aromatic phosphites; manufactured by Hoechst) and 0.16% calcium stearate 4) Polyethylene powder manufactured by Hoechst with a melt index (MF) of less than 0.1 g/10 min
I190/5) In order to demonstrate the aging resistance of the polymer compositions rendered flame retardant according to the invention, the product of Example 18 was stored at 150 DEG C. for various periods in an air circulation drying cabinet. After each storage period, they were classified according to UL-94 and the oxygen index of the specimens was determined. The results of the aging test are shown in Table 5.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

Claims (4)

[Claims] 1. A flame retardant system comprising at least 8 to 45% by weight of a phosphorus component and the monomeric triazinylpiperazine, wherein said phosphorus component is in the form of a free-flowing, powdery, poorly water-soluble Flame-retardant polymer compositions, preferably olefinic polymer and/or copolymer compositions, characterized in that ammonium polyphosphate is used, in which case powdered bis-triazinylpiperazine is used. . 2. Ammonium polyphosphate represented by the formula (NH4PO3)n has a chain length n of 200 to 1000, a phosphorus content of 31.5±0.5% by weight, and a phosphorus content of 14.5±
Flame-retardant polymer according to claim 1, characterized in that it has a nitrogen content of 0.5% by weight and a water-soluble fraction - measured in a 10% aqueous suspension at 25°C - of less than 10%. Composition. 3. Ammonium polyphosphate of the formula (NH4PO3) n having a chain length n of 200 to 1000 is microencapsulated in a melamine/formaldehyde resin, and a phosphorus content of 29.0 ± 1%, 16.5 ± 1% nitrogen content and 1 at 25°C
Flame-retardant polymer composition according to claim 1, characterized in that it has a water-soluble fraction of -9.3% or less, measured in a 0% aqueous suspension. Claim 4: General formula [Formula 1] (In the above formula, X and Y are the same or different groups -OR1
, -SR1 or NR2R3, where:
R1 is C1-C18-alkyl group, C5-
C18- cycloalkyl group, phenyl- or naphthyl group optionally substituted with inert groups or C7
- C18- represents an aralkyl group; R2 and R3 are independently C1-C3
- alkyl groups, C5 - C18- cycloalkyl groups, phenyl groups optionally substituted with inert groups -
or represents a naphthyl group or C7-C18-
represents an aralkyl group, or NR2 R3 represents a piperidinyl represented by the formula [Chemical formula 2] or a bis-represented by the formula [Chemical formula 3]
Flame-retardant polymer composition according to any one of claims 1 to 3, characterized in that triazinylpiperazine is used.